EP1205580B1 - Korrosionsbeständiges Stahlblech mit chemisch modifizierter Zinkbeschichtung - Google Patents
Korrosionsbeständiges Stahlblech mit chemisch modifizierter Zinkbeschichtung Download PDFInfo
- Publication number
- EP1205580B1 EP1205580B1 EP01125365A EP01125365A EP1205580B1 EP 1205580 B1 EP1205580 B1 EP 1205580B1 EP 01125365 A EP01125365 A EP 01125365A EP 01125365 A EP01125365 A EP 01125365A EP 1205580 B1 EP1205580 B1 EP 1205580B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- steel sheet
- acid
- layer
- converted layer
- converted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/361—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/368—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing magnesium cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/46—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing oxalates
- C23C22/47—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing oxalates containing also phosphates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12583—Component contains compound of adjacent metal
- Y10T428/1259—Oxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12611—Oxide-containing component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12611—Oxide-containing component
- Y10T428/12618—Plural oxides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12785—Group IIB metal-base component
- Y10T428/12792—Zn-base component
- Y10T428/12799—Next to Fe-base component [e.g., galvanized]
Definitions
- the present invention relates to a chemically processed steel sheet remarkably improved in corrosion resistance by generation of a converted layer with a self-repairing faculty on a surface of a zinc plating layer.
- JP 51-2419 B1 proposed a method of dipping a steel member in a chemical liquor containing magnesium or calcium molybdate
- JP 6-146003 A1 proposed a method of applying a chemical liquor, which contains a partially reduced oxide of Mo(VI) at a ratio of Mo(VI)/total Mo to 0.2-0.8, to a steel member.
- JP 11-61431 A1 proposed a method of applying a chemical liquor, which contains titanium sulfate and phosphoric acid, to a galvanized steel sheet.
- a titanium-containing layer does not exhibit a self-repairing faculty due to insolubility, although it is uniformly generated on a surface of a steel base in the same way as the chromate layer.
- the titanium-containing layer is ineffective for suppression of corrosion starting at defective parts formed during chemical conversion or plastic deformation.
- the other Cr-free converted layers are also insufficient for corrosion prevention due to poor self-repairing faculty.
- the present invention aims at provision of a processed zinc-coated steel sheet remarkably improved in corrosion resistance by generation of a converted layer, which contains insoluble or scarcely-soluble compounds useful as a barrier for insulation of a steel base from an atmosphere and soluble compounds with a self-repairing faculty for repairing damaged parts of the converted layer.
- the present invention proposed a new processed zinc-coated steel sheet comprising a steel base coated with a Zn or its alloy plating layer and a chemically converted layer, as defined in claim 1.
- a chemical liquor for generation of such a converted layer contains a manganese compound, a titanium compound, phosphoric acid or a phosphate, a fluoride and organic acids.
- the chemical liquor is adjusted at pH 1-6.
- the converted layer may further contains one or more of soluble or scarcely-soluble metal phosphates or complex phosphates.
- the soluble metal phosphate or complex phosphate may be a salt of alkali metal, alkaline earth metal or Mn.
- the scarcely-soluble metal phosphate or complex phosphate may be a salt of Al, Ti, Zr, Hf or Zn.
- the steel sheet is dried as such at 50-200°C without washing to generate a converted layer on a surface of a plating layer.
- Manganese compounds are effective components other than chromium compound, which give a self-repairing faculty to a converted layer, since these compounds are once dissolved to water in an atmosphere and then re-precipitated as scarcely-soluble compounds at defective parts of the converted layer.
- a manganese compound present in a converted layer is partially changed to a soluble component effective for realization of a self-repairing faculty.
- the inventors experimentally added various kinds of chemicals and researched effects of the chemicals on corrosion resistance.
- the inventors discovered that addition of a titanium compound to a chemical liquor for generation of a manganese compound converted layer effectively suppresses dissolution of the converted layer without weakening a self-repairing faculty.
- Improvement of corrosion resistance by addition of a titanium compound is supposed by the following reasons, and confirmed by the below mentioned examples.
- a converted layer which is generated from a manganese phosphate liquor on a surface of a zinc plating layer, is relatively porous.
- the porous layer allows permeation of corrosive components therethrough to a steel base, resulting in occurrence of corrosion.
- a converted layer when a converted layer is generated from a titanium-containing chemical liquor, pores of the converted layer are filled with titanium compounds precipitated from the chemical liquor.
- the titanium compounds are insoluble or scarcely-soluble and act as a barrier for shielding a steel base from an atmosphere.
- the chemical liquor is controlled in an acid range to dissolve the titanium salt, dissolution of Zn from a Zn or its alloy plating layer is promoted.
- the dissolved Zn is re-precipitated as zinc hydrate useful as a corrosion inhibitor at pores of the converted layer. Consequently, the converted layer is superior of corrosion resistance and exhibits a self-repairing faculty.
- the titanium compound can be dissolved without excessively falling a pH value, due to co-presence of titanium ion with manganese ion in the chemical liquor.
- a chemical liquor for generation of a converted layer containing a complex compound of Mn and Ti is an acid solution containing one or more of manganese compounds and titanium compounds.
- the manganese compound may be one or more of Mn(H 2 PO 4 ) 2 , MnCO 3 , Mn(NO 3 ) 2 , Mn(OH) 2 , MnSO 4 , MnCl 2 and Mn(C 2 H 3 O 2 ) 2 .
- the titanium compound may be one or more of K 2 TiF 6 , TiOSO 4 , (NH 4 ) 2 TiF 6 , K 2 [TiO(COO) 2 ], TiCl 4 and Ti(OH) 4 .
- the chemical liquor contains phosphoric acid or phosphate, which etches a surface of a Zn or its alloy plating layer to an activated state and changes to a scarcely-soluble phosphate effective for corrosion resistance.
- the phosphate may be manganese phosphate, sodium dihydrogenphosphate, disodium hydrogenphosphate, magnesium phosphate and ammonium dihydrogenphosphate.
- Phosphoric acid or phosphate is preferably added to the chemical liquor at a P/Mn mole ratio of 0.2-4.
- An effect of phosphoric acid or phosphate on corrosion resistance is apparently noted at a P/Mn mole ratio not less than 0.2, but an excessive P/Mn mole ratio above 4 means too-intensified etching action and instability of the chemical liquor
- An organic acid with chelating function is further added to the chemical liquor, to maintain scarcely-soluble metals such as Mn and Ti as stable metal ions.
- the organic acid may be one or more of tartaric, tannic, citric, oxalic, malonic, lactic and acetic acids.
- the organic acid is preferably added at an organic acid/Mn mole ratio of 0.05-1.
- An effect of the organic acid on chelation of metal ions for stabilization of the chemical liquor is typically noted at an organic acid/Mn mole ratio not less than 0.05, but an excessive ratio more than 1 decreases the pH value of the chemical liquor and worsens continuous processability.
- the manganese compound, the titanium compound, the phosphoric acid or phosphate, the fluoride and the organic acid are mixed together at ratios to adjust a pH value of the chemical liquor to 1-6.
- etching action of the chemical liquor on a surface of the Zn or its alloy plating layer is accelerated, and the surface of the plating layer is reformed to an activated state in a short time.
- excessive falling of the pH value below 1 causes violent dissolution of Zn from the plating layer and instability of the chemical liquor, and an excessively higher pH value above 6 also degrades stability of the chemical liquor due to precipitation of titanium compounds.
- Orthophosphates or polyphosphates of various metals may be added for incorporation of soluble or scarcely-soluble metal phosphates or complex phosphates in a converted layer.
- a soluble metal phosphate or complex phosphate is dissolved from a converted layer, reacted with Zn and Al in a steel base through defective parts of the converted layer and re-precipitated as scarcely-soluble phosphates which assist a self-repairing faculty of a titanium fluoride.
- An atmosphere is slightly acidified on dissociation of the soluble phosphate, so as to accelerate hydrolysis of the titanium fluoride, in other words generation of scarcely-soluble titanium oxide or hydroxide.
- a metal component capable of generating a soluble phosphate or complex phosphate is an alkali metal, an alkaline earth metal, Mn and so on. These metals are added as metal phosphates alone or together with phosphoric acid, polyphosphoric acid or another phosphate to the chemical liquor.
- a scarcely-soluble metal phosphate or complex phosphate is dispersed in a converted layer, resulting in elimination of defects and increase of strength.
- a metal component capable of generating a scarcely-soluble phosphate or complex phosphate is Al, Ti, Zr, Hf, Zn and so on. These metals are added as metal phosphates alone or together with phosphoric acid, polyphosphoric acid or another phosphate to the chemical liquor.
- a steel sheet coated with an Al-containing plating layer has the disadvantage that its surface is easily blackened. Such blackening is inhibited by incorporation of one or more salts of Fe, Co and Ni in the converted layer.
- a self-repairing faculty derived from fluoride and phosphate is sometimes insufficient, when big cracks are generated in the converted layer by plastic deformation of the steel sheet with a heavy work ratio.
- the self-repairing faculty is intensified by adding one or more of soluble oxoates of Mo(VI) and W(VI) to the converted layer at a great ratio. Such the oxoates exhibit the same function as Cr(VI) to repair the defective parts of the converted layer, resulting in recovery of corrosion resistance.
- the lubricant may be powdery synthetic resins, for instance polyolefin resins such as fluorocarbon polymer, polyethylene and polypropylene, styrene resins such as ABS and polystyrene, or halide resins such as vinyl chloride and vinylidene chloride.
- An inorganic substance such as silica, molybdenum disulfide, graphite and talc may be also used as the lubricant. Improvement of workability of a processed steel sheet is noted by addition of the lubricant to the converted layer at a ratio not less than 1 mass %, but excessive addition above 25 mass % impedes generation of the converted layer, resulting in degradation of corrosion resistance.
- the chemical liquor prepared as above-mentioned is spread to a Zn or its alloy plating layer formed on a steel sheet by an applicator roll, a spinner, a sprayer or the like, the steel sheet is dried as such without washing to generate a converted layer good of corrosion resistance on a surface of the plating layer.
- the chemical liquor is preferably applied at a ratio not less than 10mg/m 2 calculated as deposited Mn or at a ratio not less than 1mg/m 2 calculated as deposited valve metal for realization of sufficient corrosion resistance.
- the steel sheet which has a converted layer generated from the chemical liquor applied to a surface of a plating layer, may be dried at an ordinary temperature, but is preferably dried in a short time at a temperature of 50°C or higher accounting continuous processability. However, drying at a too-high temperature above 200°C causes thermal decomposition of organisms of a converted layer, resulting in degradation of corrosion-resistance.
- An organic paint film good of corrosion resistance may be laid on the converted layer.
- Such the paint film is formed by applying a resin paint containing one or more of olefinic resins such as urethane, epoxy, polyethylene, polypropylene and ethylene-acrylic copolymer, styrenic resins such as polystyrene, polyesters, acrylic resins or these copolymers or degenerated resins.
- the resin paint may be applied to the converted layer by an applicator roll or electrostatic atomization.
- a paint film of 0.5-5 ⁇ m in thickness is laid on the converted layer, the converted layer surpasses a conventional chromate layer in corrosion resistance.
- the converted layer can be bestowed with lubricity or weldability by laminating an organic paint film good of electric conductivity thereon.
- a steel sheet A was of 0.5mm in thickness and electroplated with Zn at a deposition ratio of 20g/m 2 per single surface.
- a steel sheet B was of 0.5mm in thickness and hot-dip coated with a Zn-6 mass % Al-3 mass % Mg alloy at a deposition ratio of 50g/m 2 per single surface.
- Chemical Liquors Nos. 1-6, 8 and 9 in which precipitates were not detected after preparation, were used for chemically processing a steel sheet A. After each chemical liquor was spread to the steel sheet, the steel sheet was carried in an electric oven and dried as such at 150°C. A converted layer generated on a surface of the Zn plating layer was analyzed by X-ray fluorescence and ESCA to measure concentration of Mn in the converted layer and to calculate ratios of Ti/Mn, P/Mn, organic acid/Mn and F/Mn. Results are shown in Table 2 .
- Corrosion-resistance of the chemically processed steel sheet was evaluated according to calculation results of the area rates as follows: an area rate not more than 5% as o ⁇ , an area rate of 5-10% as ⁇ , an area rate of 10-30% as ⁇ , an area rate of 30-50% as ⁇ and an area rate more than 50% as ⁇ .
- Results are shown in Table 2 , wherein a processed steel sheet, which had a chromate layer generated by a conventional chromating liquor (offered as ZM-3387 by Nihon Parkerizing Co., Ltd.) was testified as a comparative example under the same conditions.
- any of the converted layers generated according to the present invention was superior to a conventional chromate layer in corrosion resistance.
- the converted layer was well affinitive with a paint film formed thereon.
- the steel sheet A was used as a steel base in the above-mentioned examples, but a Zn alloy-electroplated steel sheet or other Zn or its alloy-coated steel sheet manufactured by a hot-dip or vacuum deposition process is also useful as a steel base.
- the inventors have confirmed that remarkable improvement of corrosion resistance is attained by generation of a converted layer containing complex compounds of Ti and Mn on these steel sheets.
- the chemically processed steel sheet according to the present invention as above-mentioned comprises a steel base coated with a Zn or its alloy plating layer and a a converted layer, which contains a scarcely-soluble metal compound and a soluble metal compound, generated on a surface of the plating layer.
- the scarcely-soluble metal compound acts as a barrier for insulation of the steel base from an atmosphere, and the soluble metal compound exhibits a self-repairing faculty. Defective parts of the converted layer, which are generated during plastic deformation of the steel sheet, are automatically repaired by re-precipitation of scarcely-soluble fluorides, so that the processed steel sheet still maintains excellent corrosion resistance without partial exposure of a steel base to an atmosphere even after plastic deformation.
- the processed steel sheets will be used in broad industrial fields instead of a conventional chromated steel sheet.
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Claims (3)
- Chemisch behandeltes Stahlblech, hervorragend in Korrosionsbeständigkeit, umfassend:ein Stahlgrundblech, das mit einer Plattierungsschicht aus Zn oder dessen Legierung beschichtet ist, undeine umgewandelte Schicht, die aus mindestens einer Komplexverbindung einer wasserlöslichen Mn-Verbindung mit einer wasserunlöslichen oder kaum wasserlöslichen Ti-Verbindung zusammengesetzt ist, erzeugt auf einer Oberfläche der Plattierungsschicht aus Zn oder dessen Legierung,
wobei die umgewandelte Schicht weiter eine oder mehrere organische Säuren, ausgewählt aus der Gruppe, bestehend aus Weinsäure, Gerbsäure, Zitronensäure, Oxalsäure, Malonsäure, Milchsäure, Essigsäure und/oder Salz(en) davon, enthält,
wobei die umgewandelte Schicht durch das Inkontaktbringen einer chemischen Flüssigkeit mit der Plattierungsschicht aus Zn oder dessen Legierung, die auf das Stahlblech beschichtet ist, und das Trocknen des Stahlblechs ohne Waschen erhältlich ist, wobei die chemische Flüssigkeit eine Manganverbindung, eine Titanverbindung, Phosphorsäure oder ein Phosphat, ein Fluorid und eine oder mehrere organische Säuren, ausgewählt aus der Gruppe, bestehend aus Weinsäure, Gerbsäure, Zitronensäure, Oxalsäure, Malonsäure, Milchsäure, Essigsäure und/oder Salz(en) davon, enthält und
wobei die chemische Flüssigkeit auf einen pH von 1 bis 6 eingestellt ist. - Chemisch behandeltes Stahlblech nach Anspruch 1, wobei die umgewandelte Schicht weiter ein oder mehrere Schmiermittel enthält.
- Chemisch behandeltes Stahlblech nach Anspruch 1 oder 2, wobei die umgewandelte Schicht weiter ein oder mehrere unlösliche oder lösliche Phosphate und Komplexphosphate enthält.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP05000627A EP1526190B1 (de) | 2000-11-10 | 2001-10-29 | Korrosionsbeständiger Stahlblech mit chemisch modifizierter Zinkbeschichtung |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000342938A JP3302677B2 (ja) | 2000-05-10 | 2000-11-10 | 耐食性に優れた亜鉛系めっき鋼板及び化成処理方法 |
JP2000342938 | 2000-11-10 | ||
JP2001183044A JP3302684B2 (ja) | 2000-10-16 | 2001-06-18 | 耐食性に優れた化成処理鋼板 |
JP2001183044 | 2001-06-18 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP05000627A Division EP1526190B1 (de) | 2000-11-10 | 2001-10-29 | Korrosionsbeständiger Stahlblech mit chemisch modifizierter Zinkbeschichtung |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1205580A1 EP1205580A1 (de) | 2002-05-15 |
EP1205580B1 true EP1205580B1 (de) | 2005-06-08 |
Family
ID=26603726
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP05000627A Expired - Lifetime EP1526190B1 (de) | 2000-11-10 | 2001-10-29 | Korrosionsbeständiger Stahlblech mit chemisch modifizierter Zinkbeschichtung |
EP01125365A Expired - Lifetime EP1205580B1 (de) | 2000-11-10 | 2001-10-29 | Korrosionsbeständiges Stahlblech mit chemisch modifizierter Zinkbeschichtung |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP05000627A Expired - Lifetime EP1526190B1 (de) | 2000-11-10 | 2001-10-29 | Korrosionsbeständiger Stahlblech mit chemisch modifizierter Zinkbeschichtung |
Country Status (7)
Country | Link |
---|---|
US (1) | US6544666B2 (de) |
EP (2) | EP1526190B1 (de) |
KR (1) | KR100852441B1 (de) |
CN (1) | CN1281785C (de) |
AU (1) | AU782149B2 (de) |
DE (2) | DE60111328T2 (de) |
MY (1) | MY117334A (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102008000600A1 (de) * | 2008-03-11 | 2009-09-17 | Chemetall Gmbh | Verfahren zur Beschichtung von metallischen Oberflächen mit einem Passivierungsmittel, das Passivierungsmittel und seine Verwendung |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004052093A (ja) * | 2002-07-24 | 2004-02-19 | Sanoh Industrial Co Ltd | 多層めっき自動車燃料配管部品 |
ES2448829T3 (es) * | 2002-12-24 | 2014-03-17 | Chemetall Gmbh | Agente de recubrimiento de conversión química y metal tratado en superficie |
JP4344222B2 (ja) | 2003-11-18 | 2009-10-14 | 新日本製鐵株式会社 | 化成処理金属板 |
DE102007061109B4 (de) * | 2007-12-19 | 2013-01-17 | Henkel Ag & Co. Kgaa | Behandlungslösung zum Beschichten eines Stahlbandes, ein Verfahren zum Aufbringen derselben sowie ein Stahlband mit einer Beschichtung erhalten aus der Behandlungslösung zur Verbesserung des Umformverhaltens |
JP5663915B2 (ja) * | 2009-03-31 | 2015-02-04 | Jfeスチール株式会社 | 亜鉛系めっき鋼板 |
JP5754102B2 (ja) | 2009-10-27 | 2015-07-22 | Jfeスチール株式会社 | 亜鉛系めっき鋼板 |
CN102115880B (zh) * | 2009-12-31 | 2015-10-14 | 汉高股份有限及两合公司 | 轻金属或其合金的表面处理组合物和溶液及表面处理方法 |
CN103069046B (zh) | 2010-09-29 | 2015-02-11 | 杰富意钢铁株式会社 | 镀锌系钢板的制造方法和镀锌系钢板 |
RU2462517C2 (ru) * | 2010-11-10 | 2012-09-27 | Государственное образовательное учреждение высшего профессионального образования Самарский государственный технический университет | Способ обработки поверхностей стальных деталей |
JP6022433B2 (ja) * | 2013-12-03 | 2016-11-09 | 日新製鋼株式会社 | 溶融Zn合金めっき鋼板の製造方法 |
WO2015110541A1 (de) * | 2014-01-23 | 2015-07-30 | Chemetall Gmbh | Verfahren zur beschichtung von metallischen oberflächen, derart beschichtete substrate und ihre verwendung |
US9631281B2 (en) * | 2014-12-04 | 2017-04-25 | Axalta Coating Systems Ip Co., Llc | Processes for producing a multilayer coating |
KR101696115B1 (ko) * | 2015-12-22 | 2017-01-13 | 주식회사 포스코 | 후처리 피막이 형성된 아연계 도금강판 및 그 후처리 방법 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06101061A (ja) * | 1992-09-22 | 1994-04-12 | Kobe Steel Ltd | 耐食性にすぐれた防錆処理クロメート鋼板 |
JP3278475B2 (ja) * | 1992-11-17 | 2002-04-30 | 日本パーカライジング株式会社 | 3価クロム化合物ゾル組成物、およびその製造方法 |
JP2003221680A (ja) * | 2002-01-31 | 2003-08-08 | Jfe Engineering Kk | 加工性および耐食性に優れた表面処理鋼板 |
JP2003221681A (ja) * | 2002-01-31 | 2003-08-08 | Jfe Engineering Kk | 加工性および耐食性に優れた表面処理鋼板 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS512419A (en) | 1974-06-25 | 1976-01-10 | Canon Kk | Shatsuta asochi |
FR2417537A1 (fr) * | 1978-02-21 | 1979-09-14 | Parker Ste Continentale | Composition a base d'hafnium pour inhiber la corrosion des metaux |
US4233088A (en) * | 1979-03-29 | 1980-11-11 | International Lead Zinc Research Organization, Inc. | Phosphatization of steel surfaces and metal-coated surfaces |
JPH07115002B2 (ja) | 1987-11-16 | 1995-12-13 | 日新製鋼株式会社 | 耐指紋性、導電性に優れた耐食性表面処理鋼板の製造方法 |
JPH06146003A (ja) | 1992-11-12 | 1994-05-27 | Sumitomo Metal Ind Ltd | 耐食性・塗装性に優れた表面処理金属材 |
US5449415A (en) * | 1993-07-30 | 1995-09-12 | Henkel Corporation | Composition and process for treating metals |
US5420562A (en) | 1993-09-28 | 1995-05-30 | Motorola, Inc. | Resistor having geometry for enhancing radio frequency performance |
JP3967796B2 (ja) | 1997-08-18 | 2007-08-29 | 新日本製鐵株式会社 | 表面処理金属材料 |
JP3898302B2 (ja) * | 1997-10-03 | 2007-03-28 | 日本パーカライジング株式会社 | 金属材料用表面処理剤組成物および処理方法 |
ATE302654T1 (de) * | 1997-10-14 | 2005-09-15 | Henkel Kgaa | Zusammensetzung und verfahren zur mehrzweckbehandlung von metalloberflächen |
DE19749508A1 (de) * | 1997-11-08 | 1999-05-12 | Henkel Kgaa | Korrosionsschutz von verzinkten und legierungsverzinkten Stahlbändern |
-
2001
- 2001-10-26 MY MYPI20014967A patent/MY117334A/en unknown
- 2001-10-29 EP EP05000627A patent/EP1526190B1/de not_active Expired - Lifetime
- 2001-10-29 EP EP01125365A patent/EP1205580B1/de not_active Expired - Lifetime
- 2001-10-29 DE DE60111328T patent/DE60111328T2/de not_active Expired - Lifetime
- 2001-10-29 DE DE60142190T patent/DE60142190D1/de not_active Expired - Lifetime
- 2001-11-06 KR KR1020010068787A patent/KR100852441B1/ko active IP Right Grant
- 2001-11-09 US US10/035,554 patent/US6544666B2/en not_active Expired - Lifetime
- 2001-11-09 CN CNB011346663A patent/CN1281785C/zh not_active Expired - Lifetime
- 2001-11-09 AU AU89371/01A patent/AU782149B2/en not_active Expired
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06101061A (ja) * | 1992-09-22 | 1994-04-12 | Kobe Steel Ltd | 耐食性にすぐれた防錆処理クロメート鋼板 |
JP3278475B2 (ja) * | 1992-11-17 | 2002-04-30 | 日本パーカライジング株式会社 | 3価クロム化合物ゾル組成物、およびその製造方法 |
JP2003221680A (ja) * | 2002-01-31 | 2003-08-08 | Jfe Engineering Kk | 加工性および耐食性に優れた表面処理鋼板 |
JP2003221681A (ja) * | 2002-01-31 | 2003-08-08 | Jfe Engineering Kk | 加工性および耐食性に優れた表面処理鋼板 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102008000600A1 (de) * | 2008-03-11 | 2009-09-17 | Chemetall Gmbh | Verfahren zur Beschichtung von metallischen Oberflächen mit einem Passivierungsmittel, das Passivierungsmittel und seine Verwendung |
DE102008000600B4 (de) * | 2008-03-11 | 2010-05-12 | Chemetall Gmbh | Verfahren zur Beschichtung von metallischen Oberflächen mit einem Passivierungsmittel, das Passivierungsmittel, die hiermit erzeugte Beschichtung und ihre Verwendung |
Also Published As
Publication number | Publication date |
---|---|
US6544666B2 (en) | 2003-04-08 |
CN1281785C (zh) | 2006-10-25 |
MY117334A (en) | 2004-06-30 |
EP1205580A1 (de) | 2002-05-15 |
AU782149B2 (en) | 2005-07-07 |
EP1526190B1 (de) | 2010-05-19 |
KR20020036710A (ko) | 2002-05-16 |
DE60142190D1 (de) | 2010-07-01 |
DE60111328D1 (de) | 2005-07-14 |
CN1353213A (zh) | 2002-06-12 |
DE60111328T2 (de) | 2006-03-23 |
KR100852441B1 (ko) | 2008-08-14 |
AU8937101A (en) | 2002-05-16 |
US20020090529A1 (en) | 2002-07-11 |
EP1526190A1 (de) | 2005-04-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1205580B1 (de) | Korrosionsbeständiges Stahlblech mit chemisch modifizierter Zinkbeschichtung | |
CA2632720C (en) | Wet on wet method and chrome-free acidic solution for the corrosion control treatment of steel surfaces | |
CA2206805C (en) | Zinc phosphate coating compositions containing oxime accelerators | |
WO2004055237A1 (ja) | 金属の表面処理用処理液及び表面処理方法 | |
CA2420587A1 (en) | Surface preparation agent and surface preparation method | |
EP1859930B1 (de) | Oberflächenbehandeltes metallisches material | |
CN101278075A (zh) | 含过氧化氢和螯合羧酸的磷化液 | |
JP3302677B2 (ja) | 耐食性に優れた亜鉛系めっき鋼板及び化成処理方法 | |
JP2005290551A (ja) | 成形加工後の皮膜密着性に優れた化成処理鋼板 | |
JP3302684B2 (ja) | 耐食性に優れた化成処理鋼板 | |
US6730414B2 (en) | Chemically processed steel sheet excellent in corrosion resistance | |
JP3908845B2 (ja) | 溶融亜鉛系めっき鋼板の表面処理方法 | |
SK112598A3 (en) | Zinc phosphatizing with low quantity of copper and manganese | |
KR100311062B1 (ko) | 내흑변성및내백청성이우수한아연함유금속도금강판의제조방법 | |
US7147934B2 (en) | Chemically processed steel sheet excellent in corrosion resistance | |
AU2005220243B2 (en) | A chemically processed steel sheet improved in corrosion resistance | |
JP4795647B2 (ja) | 耐食性,塗装性,接着性に優れた亜鉛系めっき鋼板 | |
SK112498A3 (en) | Zinc-phosphatizing method using low nickel and/or cobalt concentrations | |
JP4344155B2 (ja) | 表面処理亜鉛めっき鋼板および表面処理液 | |
JP3197369B2 (ja) | 亜鉛系めっき鋼板のクロメート処理の前処理方法 | |
JP3845441B2 (ja) | 表面処理鋼板およびその製造方法 | |
JP4073796B2 (ja) | 耐食性に優れた化成処理鋼板 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
17P | Request for examination filed |
Effective date: 20021107 |
|
AKX | Designation fees paid |
Designated state(s): DE FR GB |
|
17Q | First examination report despatched |
Effective date: 20030310 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE FR GB |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 60111328 Country of ref document: DE Date of ref document: 20050714 Kind code of ref document: P |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20060309 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20091022 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20091029 Year of fee payment: 9 Ref country code: GB Payment date: 20091028 Year of fee payment: 9 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20101029 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20101102 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20110630 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20101029 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 60111328 Country of ref document: DE Effective date: 20110502 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110502 |